WO2004076063A1

WO2004076063A1 - Catalyst for producing liquefied petroleum gas, process for producing the same, and process for producing liquefied petroleum gas with the catalyst

Info

Publication number: WO2004076063A1
Application number: PCT/JP2004/002202
Authority: WO
Inventors: Kaoru Fujimoto; Kenji Asami; Sachio Asaoka; Xiaohong Li
Original assignee: Japan Gas Synthesize, Ltd.
Priority date: 2003-02-26
Filing date: 2004-02-25
Publication date: 2004-09-10
Also published as: JPWO2004076063A1; US20060242904A1; CN1753727A

Abstract

A catalyst for the production of a liquefied petroleum gas which comprises a methanol synthesis catalyst ingredient and a zeolite catalyst ingredient. Carbon monoxide is reacted with hydrogen in the presence of the catalyst to produce a liquefied petroleum gas comprising propane as the main component.

Description

Specification

Liquefied petroleum gas production catalyst, method for producing the same, and liquefied petroleum gas production method using the catalyst

The present invention relates to a catalyst for producing a liquefied petroleum gas whose main component is propane by reacting carbon monoxide and hydrogen, a method for producing the catalyst, and a method for producing a liquefied petroleum gas using the catalyst About.

Liquefied petroleum gas (LPG) is obtained by compressing petroleum or natural gas hydrocarbons that exhibit a gaseous state at normal temperature and pressure, or cooling them at the same time to make them liquid. The main component is propane or butane. is there. Can be stored and transported in liquid form

LPG is characterized by its excellent portability and, unlike natural gas, which requires a pipeline for supply, can be supplied to any place in a state filled with bombs. Therefore, LPG containing propane as a main component, that is, propane gas, is widely used as fuel for home and business use. At present, even in Japan, about 25 million households (more than 50% of all households) are supplied. Propane gas is also used as industrial fuel and automotive fuel.

Conventionally, LPG has been 1) recovered from wet natural gas, 2) recovered from crude oil through the steaming (vapor pressure adjustment) process, and 3) separated and extracted from those produced in the oil refining process. It is produced by such methods.

LPG ヽ In particular, propane gas, which is used as a fuel for home and business use, is expected to be demanded in the future, and is very useful if a new production method that can be implemented industrially can be established.

As a method for producing LPG, "Selective Sentes is of LPG rom Synthes is Gas", aoru Fuj imot oeta 1., Bull. Chem. Soc. Jpn., LA, p. 3059-3060 (1985) shows that 4 wt% Pd / Si0 _2. Cu-Zn-A1 mixed oxide [Cu: Zn: Al = 40:23:37 (atomic ratio)] or Cu-based low-pressure methanol synthesis catalyst (trade name: BASF S3-85) and Si Selectivity of C 2 to C 4 paraffins from synthesis gas via methanol and dimethyl ether using a hybrid catalyst consisting of 0 ₂ / Α 1 ₂ 0 ₃ 2 7.6 high silica Y-type zeolite A method of manufacturing at 69-85% is disclosed. However, with this method, the selectivity for propane (C3) and pulp (C4) is around 63-74%, and the product is not suitable for LPG products.

Also described in the above-mentioned "Se1ectiVeSnt hesis of LPG from Synthesis Gas", Bull. Chem. Soc. Jpn., ^, P. 3059-3060 (1985). The main component of the product obtained by the above method is butane. LPG used as a fuel for domestic and commercial use is propane gas, as described above. Compared to butane gas, propane gas has the advantage that combustion can be continued at a stable and high output even at low temperatures. Household • Easy-to-liquefy fuel gas, which is widely used as a commercial fuel, industrial fuel, and automotive fuel, has a sufficiently high vapor pressure even in winter or cold regions and has a high Propane gas, which is higher in calories, is superior to pu gas. DISCLOSURE OF THE INVENTION

An object of the present invention is to provide a catalyst capable of producing liquefied petroleum gas whose main component is propane by reacting carbon monoxide and hydrogen, a method for producing the catalyst, and liquefied petroleum using the catalyst. It is to provide a method for producing gas. According to the present invention, a liquid containing propane as a main component by reacting carbon monoxide and hydrogen. The present invention provides a catalyst for producing liquefied petroleum gas, which is a catalyst used for producing liquefied petroleum gas, comprising a catalyst component for synthesis of methanol and a catalyst component for zeolite.

Further, according to the present invention, the content ratio (by mass) of the methanol synthesis catalyst component to the zeolite catalyst component is 0.5-3 [methanol synthesis catalyst component / zeolite catalyst component]. Certain of the foregoing liquefied petroleum gas production catalysts are provided.

Further, according to the present invention, the Zeorai preparative catalyst _{component, S i 0 2 / A 1} 2 0 3 molar ratio of 1 0-5 above catalyst for producing a liquefied petroleum gas is a Zeorai bets of 0 is provided . Further, according to the present invention, the liquefied petroleum gas production method according to the above, wherein the zeolite catalyst component is a medium pore zeolite or a large pore zeolite having three-dimensional expansion of pores through which reactive molecules can diffuse. A catalyst is provided.

Further, according to the present invention, there is provided the method for producing a liquefied petroleum gas production catalyst, wherein a methanol synthesis catalyst component and a zeolite catalyst component are separately prepared and mixed.

Further, according to the present invention, it is characterized in that carbon monoxide and hydrogen are reacted in the presence of the above-mentioned catalyst for producing liquefied petroleum gas to produce liquefied petroleum gas whose main component is propane. A method for producing liquefied petroleum gas is provided.

Further, according to the present invention, there is provided a liquefied petroleum gas production process for producing a liquefied petroleum gas whose main component is propane by flowing a synthetic gas through a catalyst layer containing the above-mentioned liquefied petroleum gas production catalyst. A method for producing a liquefied petroleum gas is provided. Further, according to the present invention, (1) a synthesis gas production step of producing a synthesis gas by reacting a hydrocarbon gas with water vapor;

(2) A liquefied petroleum gas production step of producing a liquefied petroleum gas whose main component is propane by flowing a synthesis gas through a catalyst layer containing the liquefied petroleum gas production catalyst. An oil and gas production method is provided. When carbon monoxide and hydrogen are reacted in the presence of the catalyst of the present invention, the following reaction occurs. Then, LPG whose main component is propane can be produced. First, methanol is synthesized from carbon monoxide and hydrogen on a methanol synthesis catalyst component. Next, the synthesized methanol is converted into a lower olefin hydrocarbon whose main component is propylene at the active site in the pores of the zeolite catalyst component. In this reaction, carbene (H0C :) is generated by dehydration of methanol, and it is considered that lower olefins are generated by polymerization of the carbene. Then, the generated lower olefins escape from the pores of the zeolite catalyst component and are rapidly hydrogenated on the methanol synthesis catalyst component to become LPG whose main component is propane.

In the presence of the catalyst of the present invention, the produced methanol quickly becomes a raw material for the next reaction (conversion of methanol to lower olefins), so that the methanol synthesis reaction is advantageous for the production system. . In the conversion reaction of methanol with dilute methanol one Le stock system holds, as a catalyst, the diffusion of the reaction molecules is limited, and a low concentration active sites, preferably _{_{S i 0 2 / A l 2}} 0 _Since a so-called high silica zeolite having a molar ratio of 10 to 50 is used, the polymerization reaction is limited to a low degree of polymerization, and lower olefins whose main component is propylene are produced. The lower olefins formed have a relatively large zeolite catalyst component, and the pores capable of diffusing the reactive molecules can easily escape from the three-dimensional pores. By being rapidly hydrogenated on the synthesis catalyst component, it becomes inert to further polymerization reactions and is stabilized. Simple day

FIG. 1 is a process flow diagram showing a main configuration of an example of an LPG manufacturing apparatus suitable for carrying out the LPG manufacturing method of the present invention.

Explanation of major signs

1 Reformer

l a Reforming catalyst layer

2 reactor 2a catalyst layer

3, 4, 5 lines

^ Ming}

The catalyst of the present invention contains a methyl synthesis catalyst component and a zeolite catalyst component. Here, the methanol synthesis catalyst component refers to a component that exhibits a catalytic action in the reaction of CO + 2 H ₂ → CH ₃ OH. The zeolite catalyst component refers to a zeolite having a catalytic action in the condensation reaction of methanol to hydrocarbon and / or the condensation reaction of dimethyl ether to hydrocarbon.

The content ratio (by mass) of the methanol synthesis catalyst component to the zeolite catalyst component is preferably 0.5 or more [methanol synthesis catalyst component / zeolite catalyst component], and 0.8 or more [methanol synthesis catalyst component / zeolite catalyst]. Catalyst component]. Further, the content ratio (by mass) of the methanol synthesis catalyst component to the zeolite catalyst component is preferably 3 or less [methanol synthesis catalyst component Z zeolite catalyst component], and 2 or less [methanol synthesis catalyst component Z zeolite. G catalyst component]. By setting the content ratio of the methanol synthesis catalyst component to the zeolite catalyst component within the above range, propane can be produced with higher selectivity and higher yield.

The methanol synthesis catalyst component has a function as a methanol synthesis catalyst, and the zeolite catalyst component is a solid acid zeolite catalyst whose acidity is adjusted to the condensation reaction of methanol and / or dimethyl ether to a hydrocarbon. Has functions. Therefore, the content ratio of the methanol synthesis catalyst component to the zeolite catalyst component is reflected in the relative ratio of the catalyst synthesis function of the present invention to the function of producing hydrocarbons from methanol. In producing liquefied petroleum gas whose main component is propane by reacting carbon monoxide and hydrogen in the present invention, carbon monoxide and hydrogen are sufficiently converted into methanol by a methanol synthesis catalyst component. Must be converted, and the generated methanol is sufficiently converted to propylene by the zeolite catalyst component. It must be converted to a certain olefin and converted to liquefied petroleum gas whose main component is propane by the methanol synthesis catalyst component.

By setting the content ratio (by mass) of the methanol synthesis catalyst component to the zeolite catalyst component to 0.5 or more [methanol synthesis catalyst component / zeolite catalyst component], higher conversion of carbon monoxide and hydrogen can be achieved. Can be converted to methanol. In addition, by setting the content ratio (mass basis) of the methanol synthesis catalyst component to the zeolite catalyst component to 0.8 or more [methanol synthesis catalyst component Z zeolite catalyst component], the generated methanol can be more selectively converted to propane. It can be converted to liquefied petroleum gas as the main component.

On the other hand, the content ratio (by mass) of the methanol synthesis catalyst component to the zeolite catalyst component is 3 or less [methanol synthesis catalyst component Z zeolite catalyst component], more preferably 2 or less [methanol synthesis catalyst component Z zeolite catalyst component]. ], The produced methanol can be converted into liquefied petroleum gas whose main component is propane at a higher conversion rate.

As the methanol synthesis catalyst component, known methanol synthesis catalysts, specifically, Cu—Zn system, Cu—Zn—Cr system, Cu—Zn—A1 system, Cu—Zn—Ag system, Cu—Zn—Mn— Cu-Zn system, such as V system, Cu-Zn-Mn-Cr system, Cu-Zn-Mn-Al-Cr system, and the one with the third component added, or ^^-! ! Type, Mo type, Ni-carbon type, and noble metal type such as Pd. Also, a commercially available methanol synthesis catalyst can be used.

The zeolite catalyst component is preferably a medium-pore zeolite or a large-pore zeolite having three-dimensional expansion of pores through which reactive molecules can diffuse. These include, for example, ZSM-5, Μ〇Μ-22Φ, Peter, Υ types. In the present invention, generally, small pore zeolite such as SA-0-34 or the like having high selectivity for the condensation reaction of methanol and / or dimethyl ether to lower olefin hydrocarbons or pores such as mordenite are used. Diffusion of reactive molecules in three dimensions Medium-pore zeolites or beta, such as ZSM-5, MCM-22, which generally show higher selectivity for the condensation of methanol and / or dimethyl ether to alkyl-substituted aromatic hydrocarbons than zeolite without Zeolites in which the diffusion of reactive molecules in pores such as large-pore zeolites such as Y-type are three-dimensional are preferred. The use of zeolite with three-dimensional diffusion of reactive molecules in the pores, such as medium-pore zeolite 1 or large-pore zeolite, allows the generated methanol to be more selectively composed mainly of propylene. It can be converted to olefins and even liquefied petroleum gas based on propane.

Here, medium pore zeolite refers to a zeolite having a pore diameter of 0.44 to 0.65 nm formed mainly by a 10-membered ring, and large pore zeolite has a pore diameter of Is a zeolite of 0.66-0.76 nm formed mainly by a 12-membered ring. The pore diameter of the zeolite catalyst component is more preferably 0.5 nm or more from the viewpoint of the selectivity of the C3 component in the gaseous product. The skeletal pore diameter of the zeolite catalyst component is more preferably 0.77 nm or less from the viewpoint of suppressing the production of liquid products such as aromatic compounds such as benzene and gasoline components such as C5 component.

As the Zeorai bets catalyst component, so-called high Shirikazeorai DOO, specifically S i 0 ₂ ZA 1 ₂ 〇 ₃ molar ratio Zeorai bets 1 0-5 0 preferred. By S I_〇 ₂ / A 1 ₂ 0 ₃ molar ratio is used high Shirikazeorai bets 1 0-5 0, Orefin to generated mainly of more selectively propylene methanol, further a main component propane Liquid petroleum gas.

The Zeorai bets catalyst component in _{_{S i 0 2 / A l 2}} 0 3 molar ratio of 1 0-5 0, or pores Zeorai bets in the spread of pores capable of spreading anti Obunko is three-dimensional Large pore zeolites are particularly preferred. As such, for example, a solid acid zeolite such as USY ゃ High Silica Type All Night is mentioned.

As the zeolite catalyst component, a solid acid zeolite as described above whose acidity is adjusted by ion exchange or the like is used.

Next, a method for producing the catalyst of the present invention will be described. As a method for producing the catalyst of the present invention, it is preferable to separately prepare a methanol synthesis catalyst component and a zeolite catalyst component, and to mix them. By separately preparing the methanol synthesis catalyst component and the zeolite catalyst component, it is easy to optimally design each composition, structure, and physical properties for each function. Generally, methyl synthesis catalysts require basicity, and zeolite catalysts require acidity. Therefore, if both catalyst components are prepared simultaneously, it becomes difficult to optimize each function.

The methanol synthesis catalyst component can be prepared by a known method, and a commercially available product can also be used. Some methanol synthesis catalysts require a reduction treatment to activate them before use. In the present invention, it is not always necessary to activate the methanol synthesis catalyst component by a reduction treatment in advance, and the methanol synthesis catalyst component and the zeolite catalyst component are mixed and molded to produce the catalyst of the present invention. Prior to the start of the reaction, a reduction treatment can be performed to activate the methanol synthesis catalyst component. The zeolite catalyst component can be prepared by a known method, and a commercially available product can also be used. Before mixing with the methanol synthesis catalyst component, the acid properties of the zeolite catalyst component may be adjusted in advance by a method such as metal ion exchange, if necessary.

The catalyst of the present invention is produced by uniformly mixing a methanol synthesis catalyst component and a zeolite catalyst component and then molding. The method of mixing and molding the two catalyst components is not particularly limited, but a dry method is preferred. When both catalyst components are mixed and molded in a wet process, compound transfer between both catalyst components, such as transfer of basic components in methanol synthesis catalyst components to acid sites in zeolite catalyst components, and neutralization This may change the physical properties and the like optimized for the respective functions of both catalyst components.

In addition, the catalyst of the present invention may contain other additive components as needed as long as the desired effect is not impaired.

Next, carbon monoxide is reacted with hydrogen using the catalyst of the present invention as described above to produce a liquefied petroleum gas, preferably a liquefied petroleum gas whose main component is propane. explain about.

The reaction temperature is preferably at least 270 ° C, more preferably at least 300 ° C, since the methanol synthesis catalyst component and the zeolite catalyst component exhibit sufficiently higher activities, respectively. . The reaction temperature is preferably 400 ° C or lower, more preferably 380 ° C or lower, in view of the limit temperature for use of the catalyst, the regulation of equilibrium, and the ease of removing and recovering the reaction heat. .

The reaction pressure is preferably 1 MPa or more, more preferably 2 MPa or more, since the methanol synthesis catalyst component exhibits a sufficiently high activity. Further, the reaction pressure is preferably 10 MPa or less, more preferably 5 MPa or less, from the viewpoint of economy.

Gas space velocity, in terms of economic efficiency, preferably 5 0 0 hr one ¹ or more, 2 0 0 0 one ¹ or more is more preferable. The gas hourly space velocity is preferably 100 000 hr- ¹ or less, since the methanol synthesis catalyst component and the zeolite catalyst component each provide a contact time showing a sufficiently higher conversion. 0 0 hr—less than ¹ is more preferable.

The concentration of carbon monoxide in the gas sent to the reactor should be at least 20 mol% from the viewpoint of securing the pressure (partial pressure) of carbon monoxide required for the reaction and improving the unit consumption of raw materials. Is more preferable, and 25 mol% or more is more preferable. The concentration of carbon monoxide in the gas fed into the reactor is preferably 40 mol% or less, more preferably 35 mol% or less, from the viewpoint that the conversion of carbon monoxide becomes sufficiently high. .

The concentration of hydrogen in the gas fed into the reactor is preferably at least 1.5 mol, more preferably at least 1.8 mol, per mol of carbon monoxide, since carbon monoxide reacts more sufficiently. Is more preferred. Further, the concentration of hydrogen in the gas fed into the reactor is preferably 3 mol or less, more preferably 2.3 mol or less, per 1 mol of carbon monoxide from the viewpoint of economy.

The gas fed into the reactor may be a mixture of carbon monoxide and hydrogen as raw material gases and carbon dioxide. By recycling the carbon dioxide emitted from the reactor or adding a corresponding amount of carbon dioxide, the reactor The production of carbon dioxide by the shift reaction from carbon monoxide in the atmosphere can be substantially reduced, and the production can be eliminated.

Further, the gas fed into the reactor may contain steam. In addition to the gas fed into the reactor, an inert gas or the like can be contained. The gas sent to the reactor can be split and sent to the reactor, thereby controlling the reaction temperature.

The reaction can be carried out in a fixed bed, a fluidized bed, a moving bed or the like, but it is preferable to select from both the control of the reaction temperature and the method for regenerating the catalyst. For example, fixed beds include quench-type reactors such as internal multi-stage quench systems, multi-tube reactors, multi-stage reactors including multiple heat exchangers, multi-stage cooling radial flow systems, and double-tube heat exchange. Other reactors such as a system, a cooling coil built-in system and a mixed flow system can be used.

The catalyst of the present invention can be used after being diluted with silica, alumina, or the like, or an inert and stable heat conductor for the purpose of controlling the temperature. Further, the catalyst of the present invention can be used by applying it to the surface of a heat exchanger for temperature control.

In the present invention, a synthesis gas can be used as a source gas. The synthesis gas can be produced by a known method, for example, by reacting a hydrocarbon gas such as natural gas (methane) with water vapor.

In the natural gas steam reforming method, for example, natural gas is desulfurized by passing it through activated carbon, and then mixed with steam or steam and carbon dioxide, and placed in a reaction tube filled with a nickel-based catalyst. The synthesis gas is produced by passing at 0 ° C and 1.5 to 2 MPa. As the reforming catalyst, an Rh-based catalyst or a Ru-based catalyst can be used in addition to the nickel-based catalyst. In order to obtain a synthesis gas having a composition suitable as a raw material gas in the present invention, it is economically advantageous to use a nickel / alumina solid solution catalyst, a molten zirconia or magnesia-supported Rh or Ru catalyst. It is preferable to reform natural gas with a low steam Z carbon ratio, specifically, a steam / carbon ratio of about 0.8 to 1.2. Synthesis gas can be produced by reacting a hydrocarbon gas such as natural gas with carbon dioxide, or by reacting a hydrocarbon gas such as natural gas with oxygen. After producing synthesis gas by water vapor reforming of natural gas, it is also possible to adjust the composition of the synthesis gas by shift reaction _{(CO + H 2 0 → C} 0 2 + H 2) as a raw material gas.

In the method for producing LPG of the present invention, a water gas produced from coal coke can be used as a raw material gas.

Next, an embodiment of the method for producing LPG of the present invention will be described with reference to the drawings.

FIG. 1 shows an example of an LPG manufacturing apparatus suitable for carrying out the LPG manufacturing method of the present invention.

First, natural gas (methane), which is a reaction raw material, is supplied to the reformer 1 via the line 3. Although not shown, steam is supplied to the line 3 for performing steam reforming. In the reformer 1, a reforming catalyst layer 1a containing a reforming catalyst is provided. Further, the reformer 1 includes a heating means (not shown) for supplying heat required for reforming. In the reformer 1, methane is reformed in the presence of a reforming catalyst, and a synthesis gas containing hydrogen and carbon monoxide is obtained.

The synthesis gas thus obtained is supplied to the reactor 2 via the line 4. The reactor 2 is provided with a catalyst layer 2a containing the catalyst of the present invention. In the reactor 2, a hydrocarbon gas whose main component is propane is synthesized from the synthesis gas in the presence of the catalyst of the present invention.

The synthesized hydrocarbon gas is pressurized and cooled after removing water and the like as necessary, and LPG as a product is obtained from the line 5. LPG may remove hydrogen or the like by gas-liquid separation or the like.

Although not shown, the LPG manufacturing apparatus is provided with a booster, a heat exchanger, a valve, an instrumentation control device, and the like as necessary.

Also, a gas such as carbon dioxide is added to the synthesis gas obtained in the reformer 1 It can also be supplied to the reactor 2. Further, hydrogen or carbon monoxide may be further added to the synthesis gas obtained in the reformer 1, or the composition may be adjusted by a shift reaction and supplied to the reactor 2.

According to the method for producing LPG of the present invention, the content of LPG whose main component is propane, specifically, the content of propane is at least 38 mol%, more preferably at least 40 mol%, particularly at least 55 mol% (100 mol%). LPG (including mol%) can be produced. The LPG produced according to the present invention has a composition suitable for propane gas, which is widely used as a fuel for home and business use. Example

Hereinafter, the present invention will be described in more detail with reference to Examples. Note that the present invention is not limited to these examples.

(Example 1)

(Production of catalyst)

As a methanol synthesis catalyst component, a commercially available Cu—Zn-based methanol synthesis catalyst (manufactured by Nippon Zudohemie Co., Ltd.) that was mechanically powdered was used. The Zeorai preparative catalyst _{_{Ingredients, S i0 2 / Al 2 0}} 3 molar ratio which is separately prepared is 1 2.2 proton type U SY Zeorai preparative (skeletal pore diameter: 0. 74 nm) powder was used.

This catalyst synthesis component was uniformly mixed with the same weight of zeolite catalyst component, and the mixture was pressed and sized, and then reduced in a hydrogen stream at 300 ° C for 3 hours to obtain a catalyst.

(Manufacture of LPG)

The prepared catalyst was filled in a reaction tube, and a raw material gas having a composition of 66.7 mol% of hydrogen and 33.3 mol% of carbon monoxide was passed. The reaction conditions, reaction temperature 325 ° C, reaction pressure 2. a 1 MP aヽgas hourly space velocity 3000 hr ^1. Analysis of the product by gas chromatography showed that the conversion of carbon monoxide to hydrocarbons was 38%. In addition, 76% of the generated hydrocarbon gas is propane and The proportion of propane and butane was 55% for propane and 45% for butane on a carbon basis.

(Example 2)

(Production of catalyst)

As Zeorai DOO catalyst component, separately prepared S i0 _₂ / Al ₂ 0 ₃ molar ratio of 37.1 proton-type base Isseki Zeorai Doo (pore diameter: minor 0.64 abdomen, the long diameter 0. 76 nm) powder A catalyst was obtained in the same manner as in Example 1 except that the catalyst was used.

(Manufacture of LPG)

When a reaction was carried out in the same manner as in Example 1 using the prepared catalyst, the conversion of carbon monoxide to hydrocarbon was 32%. In addition, 73% of the generated hydrocarbon gas was propane and butane on a carbon basis, and the breakdown of propane and butane was 51% for propane and 49% for butane on a carbon basis.

(Example 3)

(Production of catalyst)

As Zeorai DOO catalyst component, separately prepared S i0 _₂ / Al ₂ 0 ₃ molar ratio of 16.9 proton type Morudenai Tozeorai Application: except for using (pore size minor 0. 65 nm, major axis 0. 70 nm) powder Was obtained in the same manner as in Example 1.

(Manufacture of LPG)

When a reaction was carried out in the same manner as in Example 1 using the prepared catalyst, the conversion of carbon monoxide into hydrocarbons was 5%. Propane and butane accounted for 40% of the generated hydrocarbon gas on a carbon basis, and the breakdown of propane and butane was 28% for propane and 72% for butane on a carbon basis.

(Example 4)

(Production of catalyst)

As Zeorai DOO catalyst component, separately prepared S i0 _₂ / Al ₂ 0 ₃ molar ratio of 14.5 proton type ZSM 5 Zeorai bets: a (pore size minor 0. 53 nm, major axis 0. 5 6 nm) powder A catalyst was obtained in the same manner as in Example 1 except that the catalyst was used. (Manufacture of LPG)

Using the prepared catalyst, the reaction was carried out in the same manner as in Example 1 except that 0.08 was added in a molar ratio of carbon dioxide to the raw material gas. The conversion of carbon monoxide to hydrocarbon was 40%. %Met. Propane and butane accounted for 56% of the generated hydrocarbon gas on a carbon basis, and the breakdown of propane and butane was 56% for propane and 44% for butane on a carbon basis.

(Example 5)

(Production of catalyst)

As Zeorai DOO catalyst component, separately prepared S i0 _₂ / Al ₂ 0 ₃ molar ratio of proton type Z SM- 5 Zeorai bets 54.5 (pore diameter: minor 0.5311111, diameter 0. 5 6 nm) powder Except for using, a catalyst was obtained in the same manner as in Example 1.

(Manufacture of LPG)

When a reaction was carried out in the same manner as in Example 4 using the prepared catalyst, the conversion of carbon monoxide to hydrocarbon was 3%. Propane and butane accounted for 7% of the generated hydrocarbon gas on a carbon basis. Propane and butane were 100% propane and 0% butane on a carbon basis. Available items

As described above, by using the catalyst of the present invention, liquefied petroleum gas whose main component is propane can be produced by reacting carbon monoxide and hydrogen.

Claims

The scope of the claims

1. A catalyst used in producing liquefied petroleum gas containing propane as a main component by reacting carbon monoxide with hydrogen.

A liquefied petroleum gas production catalyst comprising a methanol synthesis catalyst component and a zeolite catalyst component.

2. The liquefied petroleum gas production according to claim 1, wherein a content ratio (by mass) of the methanol synthesis catalyst component to the zeolite catalyst component is 0.5 to 3 [methanol synthesis catalyst component Z zeolite catalyst component]. Catalyst.

3. The zeolite preparative catalyst component, S I_〇 ₂ ZA 1 ₂ 0 ₃ molar ratio of 1 0-5 0 Ze Orai preparative liquefied petroleum gas production catalyst according to claim 1.

4. The liquefied petroleum gas production according to claim 1, wherein the zeolite catalyst component is a medium pore zeolite or a large pore zeolite having three-dimensional expansion of pores through which reactive molecules can diffuse. catalyst.

5. The method for producing a liquefied petroleum gas production catalyst according to claim 1, wherein a methanol synthesis catalyst component and a zeolite catalyst component are separately prepared and mixed.

6. A liquefied petroleum gas characterized by reacting carbon monoxide and hydrogen in the presence of the liquefied petroleum gas production catalyst according to claim 1 to produce a liquefied petroleum gas whose main component is propane. Production method.

7. A liquefied petroleum gas produced by circulating a synthesis gas through a catalyst layer containing the liquefied petroleum gas production catalyst according to claim 1 to produce a liquefied petroleum gas whose main component is propane. A method for producing liquefied petroleum gas, comprising a production process.

8. (1) A synthesis gas production process for producing a synthesis gas by reacting a hydrocarbon gas with steam.

(2) A liquefied petroleum gas production process for producing a liquefied petroleum gas whose main component is propane by flowing synthesis gas through a catalyst layer containing the liquefied petroleum gas production catalyst according to claim 1.

A method for producing a liquefied petroleum gas, comprising:

9. The method for producing a liquefied petroleum gas according to any one of claims 6 to 8, wherein the content of propane in the produced liquefied petroleum gas is 38 mol% or more.